Spin bath additives



United States Patent 3,298,962 SPIN BATH ADDITIVES Max E. Chiddix, Easton, and Earl P. Williams, Pen Argyl,

Pa., and Robert L. Sundberg, Martinsville, N.J., assignals to General Aniline & Film Corporation, New York,.N.Y., a corporation of Delaware No Drawing. Filed Dec. 29, 1960, Ser. No. 79,170 Claims. (Cl. 252-357) This application is a continuation in part of our application Serial No. 398,212, filed December 14, 1953, now abandoned.

This invention relates to the production of improved spin bath additives and to the spin bath containing same.

In the manufacture of synthetic fibers, yarns, filaments, films, and thelike, by the wet spinning process, a solution of a synthetic polymeric substance is spun or extruded through an orificeinto a spin bath in which the polymeric substance is coagulated or precipitated in the desired form. These spin baths are in many cases highly acid in nature and contain varying amounts of salts and other additives depending upon the material being spun, the use .to which it is to be put, the form in which it is desired to be produced, and the like. During the filament spinning operation, there is a common tendency for the spinnerets to become incrusted and clogged, causing cratering of the spinneret leading to a diminished or uneven cross-section of the spun filament or tearing of the spun material, and for the spun material to pick up staticcharges, and sludge, sulfur, and/or salt deposits. Various additives have been proposed in the past to counteract such tendencies, but have not been found entirely satisfactory due in part to their lack of stability in the acidic spin baths. The rayon industry particularly needs anticratering and sludge dispersing additives for the spin bath which are stable to higher temperatures such as 80 to 100 C. This would make possible a higher production rate in continuous rayon spinning and make it cheaper to concentrate and renew the spent spin bath acid.

It is an object of this invention to provide improved spin bath additives which act to prevent incrustation and clogging of spinnerets (cratering) and formation of static charges, sulfur, sludge, or salt deposits on the spun material or on the equipment. Another object of this invention is to provide spin bath additives of the More mentioned type having improved stability in aqueous acidic spin baths, particularly at higher temperatures. Other objects and advantages will appear as the description proceeds.

Thepattainment of the aforementioned objects is made possible by the instant invention, in which an improved spin bath additive may be prepared by admixture of an oxyalkylenated higher molecular weight amine with the product of reaction of one mole of a polyamine of the formula H(NHR),,NH in which R is an alkylene radical containing 2 to 6 carbon atoms and x has a value notes hydrogen atoms attached to nitrogen.

Polyamines operative for acylation in accordance with the instant invention include those of the above formula in which R is ethylene, propylene, hexamethylene, isopropylene, isobutylene and the like, and x has a value of 1 to 6. By way of example, such compounds include triethylene tetramine, tetraethylene pentamine, pentaethylene hexarnine, dipropylene triamine, tripropylene Patented Jan. 17, 1967 ice tetramine, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, the crude amine mixture resulting from the reaction of ammonia with ethylene dichloride or propylene dichloride or the like, and particularly diethylene triamine, including mixtures of two or more of such polyamines.

As the source of the tall oil or rosin acids to be reacted with the polyamine, there may be mentioned wood and gum rosin, crude and refined tall oil, and the like. Crude tall oil varies samewhat in composition but usually contains about 30 to 46 percent of rosin acids, 47 to 60 percent of unsaturated higher fatty acids, and 4 to 12 percent of unsaponifiable constitutents such as sterols, and the like. Certain refined tall oils contain a higher percentage of rosin acids because the lower boiling fatty acids have 'been removed by distillation.

The reaction between the polyamine and tall oil or rosin acids involves replacement of N-hydrogen atoms by acyl groups, and is accordingly described herein and the appended claims as an N-acylation reaction, the acyl replacement occurring in a primary amino group and/or in a secondary amino group of the polyamine. It will of course be understood that the product of this N-acyla tion reaction is a complex mixture whose composition depends upon the composition of the polyamine, the composition of the rosin or tall oil, the molar ratio of the reactants, and the like. Thus, when one mole of a polyalkylene polyamine is reacted with one mole or less of tall oil, the product is essentially a mixture of the mono-N-fatty acid acyl polyalkylene polyamine and mono-N-rosin acid acyl polyalkylene polyamine together with unreacted polyalkylene polyamine, and the like. The mixture produced would be correspondingly more complex if a mixture of polyalkylene polyamine were employed as reactants. When one mole of polyalkylene polyamine is reacted with two moles of tall oil, the product is essentially a mixture of di-N,N-fatty acid acyl polyalkylene polyamine, di-N,N-rosin acid acyl polyalkylene polyamine, di-N,N'-acyl polyalkylene polyamine derivatives in which one acyl radical is a fatty acid radical and the other acyl radical is a rosin acid radical, together with small amounts of unreacted polyalkylene polyamine and the like. Further, there will obviously be small proportions of mono-acyl and tri-acyl derivatives in the mixture thus produced. The preferred N-acylated polyamine for use in this invention is the reaction product of 2.45 moles of polyamine mixture with about 1.5 molecular equivalents of tall oil acyls, reaction products of one mole of polyamine with /2 to two molecular equivalents of tall oil acyls being most generally employed. Since diethylene triamine contains 5 replaceable N-hydrogen atoms, the N-acylated derivative will theoretically contain 3 remaining replaceable N-hydrogren atoms available for condensation with the alkylene oxide. The acylation of polyamines to form these aminoamides may be carried out at temperatures ranging from about 185 to 210 C. for a sufiicient time to complete the reaction.

The N-acylated polyamine product is then reacted with an amount of an alkylene oxide in excess of that necessary to condense with all the remaining replaceable N- hydrogen atoms therein. The excess alkylene oxide will react with the previously formed hydroxyalkyl groups to produce a derivative having at least one polyoxyalkylene radical. In general, at least 4 and up to 40 moles of alkylene oxide should be reacted with each mole of the N-acylated polyamine, relatively greater amounts of alkylene oxide being preferably used as the degree of acylation increases. The condensation may be carried out in well known manner in the presence of an alkaline condensing agent such as sodium hydroxide or potassium hydroxide, or the like, at temperatures of from about C. to 170 C. and if desired under pressure. In some cases, however, particularly where a relatively small amount of alklene oxide is being reacted, it may be desirable to carry out the oxyalkylenation in the absence of an alkaline catalyst since under these conditions the amino groups in the N-acylated polyamine are more reactive than hydroxy groups whereby condensation with all remaining replaceable N-hydrogens is assured. If desired, the initial stage of the oxyalkylenation may be carried out in the absence of a catalyst to promote replacement of all remaining replaceable N-hydrogen atoms with hydroxy alkyl groups, after which a catalyst may be added to promote further reaction of the alkylene oxide with the hydroxy alkyl groups to produce the desired number of polyoxyalkylenated chains of the desired length. The preferred alkylene oxide is ethylene oxide although propylene oxide, butylene oxide and the like, may also be employed. These products are preferred which contain about to 35 oxyalkylene units per mole of oxyalkylenated acylated polyamine.

It will be understood that the oxyalkylenation reaction results in a mixture which is even more complex than the mixture containing the acylated polyamine with which the alkylene oxide is reacted. Thus, the mixture resulting from the oxyalkylenation reaction may contain one or several polyoxyalkylene chains of varying lengths distributed among one or more compounds. The mixture will generally contain varying amounts of compounds having a greater or smaller number of oxyalkylene units than the average of such units as indicated by analytical determination.

In general, the preferred acylating agents are, in addition to rosin acids, those refined tall oil acids containing at least 50% and preferably at least 70% by weight of rosin acids.

According to the invention, to the polyoxyalkylenated acylated polyamine reaction product above described there is added a condensation product of at least one mole of an alkylene oxide of 2 to 3 carbon atoms with a member of the group consisting of primary and secondary aliphatic and alicyclic amines containing at least 8 carbon atoms, in proportions of about 0.1 to 10 and preferably about 0.02 to 2 parts of the oxyalkylenated amine for each part by weight of the polyoxyalkylenated acylated polyamine. These oxyalkylenated amines may be derived from such amines as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylarnine, n-octadecylamine, octadecenylamine, octadecadienylamine, didodecylamine, N-methyldodecylamine, isooctylamine, isopentadecylamine, amines prepared from olefins and polyolefins by the addition of HCN in aqueous acid followed by hydrolysis, amines prepared by amination of the polypropylene, polybutene or propylene-butylene mixtures, amines prepared from oxoalcohols obtained by the Oxo reaction of C0 and H on polypropylenes, polybutylenes and propylenebutylene mixtures, amines prepared by reduction of saturated or unsaturated fatty acid amines or nitriles, alicyclic amines such as dicyclohexylamine, N- butyl-N-cyclohexylamine, and primary amines derived from rosin or its hydrogenated or dehydrogenated derivatives, e.g. by replacing carboxyl groups with an amino methyl group in abietic, hydroabietic or dehydroabietic acid, or by introducing a primary amino group into the nucleus of abietyl compounds and their hydrogenated or dehydrogenated derivatives, e.g. by nitration and reduction as disclosed in U.S.P. 2,240,936 or by halogenation and amination as disclosed in U.S.P. 2,367,001 and the like, or mixtures thereof. These amines may be oxyalkylenated by reaction with from 1 to about 40 moles of an alkylene oxide in the same manner as described above for the preparation of the polyoxyalkylenated acylated polyamine. The reaction product of a long chain aliphatic primary amine with from 3 to moles of ethylene oxide is preferred.

The described surface active composition containing the polyoxyalkylenated acylated polyamine reaction product in admixture with the defined oxyalkylenated amine has been found to be highly effective in acidic spin baths containing up to 15 percent or more of a mineral acid such as sulfuric acid and the like, as employed in the manufacture of extruded products from solutions of cellulose xanthate, cuprammonium cellulose and other cellulosic compositions, casein, zein, albumen and other proteinaceous compositions, and the like. Examples of these products include cellophane, viscose rayon, and a number of other artificial fibers, filaments, films and the like. In addition to their function in preventing incrustation and clogging of spinnerets, in reducing static charges, sulfur, sludge, or salt incrustations on the spun materials, and cratering the spinnerets or tearing of the spun materials, the above described compositions of this invention have been found to be unusually stable to the high temperatures sometimes found necessary in the use of spin baths. While usually operated at 40 to 60 C. higher temperatures are often desirable for spinning and other acid regeneration operations. However, these high tem peratures cause considerable difficulty due to decomposition of the spin bath additives usually employed. The compositions of this invention as described above have been found to be stable at C. for two weeks or more in a typical rayon spin bath composition comprising about 10 percent sulfuric acid monohydrate, 17 percent sodium sulfate, and 1.5 percent Zinc sulfate by weight in aqueous solution.

It will be understood that the amounts of spin bath additives of this invention to be employed in any particular spin bath will vary depending upon the character of the material being spun, speed of operation, acidity of spin bath and the like. In general, they are employed in concentrations ranging from about 1 to 1000 p.p.m. (parts per million by weight of spin bath). Thus, spin baths employed in producing textile filament yarns usual ly contain about 25 to 75 p.p.m. of the additive (either the oxyalkylated acylated polyamine or its mixture with the oxyalkylated amine), baths employed for textile staple yarns about 40 to p.p.m., and tire cords about 400 to 500 p.p.m.

The additives of this invention should be either soluble or readily dispersible in the spin bath. Some additives may be insoluble as the base but are solubilized as salts in the acid spin baths.

The polyoxyalkylenated acylated polyamines and their mixtures with oxyalkylenated higher aliphatic and alicyclic amines as above described have been found to constitute highly efiicient and stable additives when employed in aqueous acidic spin baths. In addition, their surface activity promotes their use in other large fields of the technical arts. For instance, they can be used as wetting agents for converting liquid or solid substances which per se are insoluble in water (such as hydrocarbons, higher alcohols, oils, fats, waxes and resins) into creamy emulsions, clear solutions or fine, stable dispersions; for falling textiles; as cleansing agents in hard water; in tanning and mordanting processes; as a means for improving the absorptive power of fibrous bodies; and as an aid in softening baths for hides and skins.

In addition, these products are valuable in emulsifier systems of insecticide compositions and agricultural sprays such as DDT, 2,4-D, toxaphene, chlordane, dormant or mineral oil sprays, nicotine sulfate, dieldrin, aldrin, lindane, B.H.C., heptachlor, I.P.C., chloro I.P.C., methoxychlor, etc.

These products are valuable for use as additives to petroleum products, as additives for fuel oils, hydraulic fluids, lubricating oils, cutting oils, greases, as additives to the water or brine used for oil recovery from oil-bearin g strata by flooding techniques.

Other valuable uses are in metal cleaning compositions. dry cleaning compositions, froth flotation agents, additives for road building materials, as air entraining agents for concrete or cement; additives to asphalt compositions,

plasticizers and modifiers for vinyl plastics, alkyl resins,

phenolformaldehyde resins, and other types of polymerictype plastic materials; for incorporation into adhesives, paint, linoleum; for use in bonding agents usedin various insulating-and building materials; as additives to pulp slurries toiaid the beating operation in papermaking.

These products are also useful as emulsifiers for emulsion polymerization, as mercerizing assistants, wetting agents, rewetting agents, dispersing agents, detergents, penetrating agents, softening agents, cutting oils, dishwashing agents, anti-static agents,.disinfectants, insecticides, mothproofing agents, bacteriocides, fungicidesand biocidesa 7 They are useful in the rayon industry as additives to the dope as aids in clarifying viscose rayon. They are of value in hydraulic fluids to improve viscosity characteristics.

Theseproducts are especially useful in breaking petroleurn emulsions. They may be used to break emulsions of crude petroleum and salt water as obtained from oil wells, or to prevent water-in-oil emulsions resulting from acidization of oil wells by introducing the agent into the well, or to break or prevent emulsions which would result from: a water flooding process for recovering oil from oilbearing strata. They may also be used to break emuls'ions encountered in a petroleum refining process.

They are useful as corrosion inhibitors, as rust inhibitors, in the protection of metals especially ferrous metals, in acid pickling baths, in acid cleaning compositions, and in electro-plating baths.

Other valuable uses are as solvents, as lubricants, as greases, and stufiing agents.

The following examples of this invention are given for illustrative purposes only and are not to be regarded as limitative. Parts are by Weight unless otherwise indicated.

Example 1 A mixture of 480 g. (1.5 moles) of Neo-Fats D-242 (Armour), 150 g. (1.45 moles) diethylenetriamine, and 150 g. (1.0 mole) triethylenetetramine was heated in a flask at 190-205 C. for 12 hours. Twenty-seven milliliters of aqueous distillate came off which contained approximately 1 gram of amine (calculated as diethylenetriamine).

The above N-acylated polyamine mixture was reacted with. twice its weight of ethylene oxide (34 moles) in the presence of a small amount of sodium hydroxide catalyst (0.3% of the weight of said mixture) at 135-140 C. and 25-30 p.s.i. for 8 hours.

The product was Water-soluble. The compositions in the. examples below were tested in the following simulated spin bath composition (parts by weight) Percent Sulfuric acid (100%) Sodium sulfate 17 Zinc sulfate 1.5

Water 71.

l Example 2 Eight hundred thirteen grams (3 moles) Armeen TD (Armour & Co.) were placed in an autoclave and heated to 90 C. Small portions of ethylene oxide were added to keep the pressure at 25-30 p.s.i. until a total of 396 grams (9 moles) ethylene oxide had been added. The temperature was kept at 90-100 C. Reaction time was 3 hours.

Seven hundred thirty-one grams of the above reaction product of Armeen TD with three moles ethylene oxide (about 1.8 moles) and 647 g. (0.65 molar equivalent of acyl) of the tall oil product from 'Example 1 were well mixed.

One drop of this product was dissolved in 10 cc. of he simulated spin bath described in Example 1 and heated 6 at 100 C. After 120 hours at 100 C. there was no decomposition apparent. After 144 hours at 100 C. there was some well dispersed cloudiness, but the mixture clarified upon cooling.

Example 3 Example 4 To 294 g. (0.29 molar equivalents of acyl) of the product obtained in Example 1 there was added (and well mixed) 173 g. (0.37 mole) of the reaction product of Armeen TD with five moles ethylene oxide.

One drop of this mixture in 10 cc. of the simulated spin bath described in Example 1 was stable for 72 hours at 60 C., 120 hours at C. and became slightly hazy after 24 hours at C.

Example 5 To 32.7 g. (0.33 molar equivalents of acyl) of the reaction product from Example 1 there was added with stirring, 21 g. (.02 mole) of the reaction product of Armeen SD (Armour) and 15.2 moles ethylene oxide.

One drop of this mixture in 10 cc. of the simulated spin bath described in Example 1 was stable and clear after 72 hours at 60 C. and then hours at 80 C. After an additional 5 hours at 100 C. the solution became cloudy.

Example 6 To 1600 g. (5 moles) of Neo-Fat D-242 there was added 150 g. (1 mole) triethylenetetramine and 193 g. (1 mole) tetraethylenepentamine. The resulting mixture was heated at 200 C. for 12 hours while distilling off water formed during the reaction.

The above N-acylated polyamine mixture was placed in an autoclave and ethylene oxide added portionwise at C. in the presence of about 0.1% of NaOH by weight of said mixture until a total of 704 g. (16 moles) of ethylene oxide had reacted.

A mixture of 1 part of the above product with 2 parts by weight of the reaction product of lauryl amine and five moles ethylene oxide was stable at 80 C. for 24 hours in the simulated spin bath described in Example 1 (at 500 ppm. concentration of the above product in the spin bath).

Example 7 A mixture of 320 g. (1.0 mole) Neo-Fat D-242, and 120 g. (2.0 moles) ethylenediamine was heated in an autoclave at 200 C. for 12 hours in the presence of 50 g. silica gel. The N-acylated polyamine mixture was filtered to remove the hydrated silica gel and then treated in the presence of about 0.1% KOH by weight of said mixture with 581 g. (10 moles) propylene oxide added portionwise at 120 C. to the mixture in an autoclave. The pressure during the propylene oxide reaction did not exceed 25 p.s.i.

One drop of a mixture of 1 part of the above product and 1 part of the reaction product of hexadecylamine and 15 moles ethylene oxide was added to 10 cc. of the simulated spin bath described in Example 1. The product remained stable after 3 days at 80 C.

In the above examples, Neo-Fat D-242 is a refined tall oil containing about 70 percent by weight of rosin acids, and 30 percent of saturated higher fatty acids. Armeen TD is a commercially available amine mixture containing about 30 percent by weight of hexadecylamine, 25 percent of octadecylamine, and 45 percent of octadecenylamine.

Armeen SD is a commercially available amine mixture containing about 10% of the hexadecylamine, 10% of octadecylamine, 35% of octadecenylamine, and 45% of octadecadienylamine.

Various modifications and variations of this invention will be obvious to the person skilled in the art and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the appended claims.

We claim:

1. A surface active composition consisting essentially of (A) a condensation product of at least 1 mole of alkylene oxide of 2 to 3 carbon atoms with a member of the group consisting of primary and secondary aliphatic and alicyclic amines containing at least 8 carbon atoms and (B) a reaction product prepared by reacting 1 mole of a polyamine of the formula H(NHR) NH in which *R is an alkylene radical containing 2 to 6 carbon atoms and x has a value of 1 to 6, with about 0.2x to x molecular equivalents of an acylating agent selected from the group consisting of rosin acids and refined tall oil containing at least 50% by Weight of rosin acids, and then reacting the resulting N-acylated polyamine product in the presence of an alkali catalyst with up to about 40 moles, per mole of said product, and more than suflicient alkylene oxide of 2 to 4 carbon atoms to condense with all the remaining replaceable N-hydrogen atoms therein, component (A) being present in proportions of about 0.1 to 10 parts for each part by weight of component (B).

2. A composition as defined in claim 1 wherein the said polyamine is diethylene triamine.

3. A composition as defined in claim 1 wherein the said polyamine is triethylene tetramine.

4. A composition as defined in claim 1 wherein the said polyamine is tetraethylene pentamine.

5. A composition as defined in claim 1 in which said polyamine is ethylene diamine.

6. A composition as defined in claim 1 in which said alkylene oxides are ethylene oxides.

7. A composition as defined in claim 1 wherein about 4 to 40 moles of alkylene oxide are employed for each mole of said N-acylated polyamine.

8. A composition as defined in claim 1 wherein about 1 to 40 moles of alkylene oxide are employed for each mole of said amine containing at least 8 carbon atoms.

9. A composition as defined in claim 1 wherein said condensation product is the condensation product of a long chain aliphatic primary amine with about 3 to 15 moles of ethylene oxide.

10. An aqueous acidic solution specially adapted for use as a spin bath for coagulating synthetic fibers and films containing about 1 to 1000 ppm. by weight of a com- 20 position as defined in claim 1.

References Cited by the Examiner UNITED' STATES PATENTS LEON D. ROSDOL, Primary Examiner.

JULIUS GREENWALD, Examiner.

I. R. SEILER, J. T. FEDIGAN, Assistant Examiner. 

1. A SURFACE ACTIVE COMPOSITION CONSISTING ESSENTIALLY OF (A) A CONDENSATION PRODUCT OF AT LEAST 1 MOLE OF ALKYLENE OXIDE OF 2 TO 3 CARBON ATOMS WITH A MEMBER OF THE GROUP CONSISTING OF PRIMARY AND SECONDARY ALIPHATIC AND ALICYCLIC AMINES CONTAINING AT LEAST B CARBON ATOMS AND (B) A REACTION PRODUCT PREPARED BY REACTING 1 MOLE OF A POLYAMINE OF THE FORMULA H(NHR)XNH2, IN WHIC R IS AN ALKYLENE RADICAL CONTAINING 2 TO 6 CARBON ATOMS AND X HAS A VALUE OF 1 TO 6, WITH ABOUT 0.2X TO X MOLECULAR EQUIVALENTS OF AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF ROSIN ACIDS AND REFINED TALL OIL CONTAINING AT LEAST 50% BY WEIGHT OF ROSIN ACIDS, AND THEN REACTING THE RESULTING N-ACYLATED POLYAMINE PRODUCT IN THE PRESENCE OF AN ALKALI CATALYST WITH UP TO ABOUT 40 MOLES, PER MOLE OF SAID PRODUCT, AND MORE THAN SUFFICIENT ALKYLENE OXIDE OF 2 TO 4 CARBON ATOMS TO CONDENSE WITH ALL THE REMAINING REPLACEABLE N-HYDROGEN ATOMS THEREIN, COMPONENT (A) BEING PRESENT IN PROPORTIONS OF ABOUT 0.1 TO 10 PARTS FOR EACH PART BY WEIGHT OF COMPONENT (B). 